CN105479659A - Complex of metal and plastic and manufacturing method of complex - Google Patents

Complex of metal and plastic and manufacturing method of complex Download PDF

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Publication number
CN105479659A
CN105479659A CN201510219593.5A CN201510219593A CN105479659A CN 105479659 A CN105479659 A CN 105479659A CN 201510219593 A CN201510219593 A CN 201510219593A CN 105479659 A CN105479659 A CN 105479659A
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CN
China
Prior art keywords
plastic material
hardware
complex
faying face
plastic
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Granted
Application number
CN201510219593.5A
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Chinese (zh)
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CN105479659B (en
Inventor
刘柳
戴天骄
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Sonim Technologies Shenzhen Ltd
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Sonim Technologies Shenzhen Ltd
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Priority to CN201510219593.5A priority Critical patent/CN105479659B/en
Priority to US14/984,904 priority patent/US20160318283A1/en
Publication of CN105479659A publication Critical patent/CN105479659A/en
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Publication of CN105479659B publication Critical patent/CN105479659B/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
    • B29C2045/14237—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure the inserts being deformed or preformed outside the mould or mould cavity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C2045/1486—Details, accessories and auxiliary operations
    • B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0085—Copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/003—Layered products comprising a metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/44—Number of layers variable across the laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a complex of metal and plastic and a manufacturing method of the complex. The complex is formed by combining a metal member, of which a combining surface has at least a part of area in a nanoscale concave-convex structure after chemical treatment, with a plastic material; the metal member and the plastic material are tightly combined in an inserting structure in the area; the metal member comprises a metal material member or an alloy material member; the plastic material mainly contains polyether block amide, and is a single-layer or layered structure. Corresponding combining and treatment technologies are matched specifically for the characteristics of the selected plastic material, so that a binding force between metal and plastic is excellent, the sealing characteristic to a certain extent is provided, the impact resistance is excellent, and the appearance decorative effect is diversified.

Description

The complex of metal and plastic cement and manufacture method thereof
Technical field
The present invention relates to the manufacturing technology that metal is integrated with plastic material, the metal that especially can provide waterproof and dustproof and shockproof effect about a kind of and plastic compound and manufacture method thereof.
Background technology
Along with manufacturing development and extension, by the technology of metal with plastic material (macromolecular material such as resin, elastomer) integrated compound, at parts such as automobile, domestic electrification goods, industrial equipments, and even the wide industrial field such as the manufacturing industry of personal daily goods has very large demand.And Manufacturing Technology Development is by plastic effective combination of the intensity of metal and rigidity and plastic material, provides more wide in range application.Metal can be realized by feasible technological means to combine with the integrated of plastic material, for the requirement of combination performance, the bond strength (can not separate easily) between the two should be met, also should meet the two compactness combined (namely, preventing dust water-based), and utilize plastic material carry out coated to the portion of exposing of hardware and adhere to, also improve the processing characteristics of this base part further.For these demands, relevant investigation and application is also in the news successively.
It is the problem be concerned all the time that the bond strength of hardware and plastic material (plastic) and tight ness rating promote, consider the impact of manufacture/environment for use and the producer and the aging of plastic cement may be accelerated, select not use the more reasonably associated methods of bonding agent to become the pursuit of more producers, therefore injection moulding combination technology is also widely used.Such as, disclose a kind of by integrated with thermoplastic resin composition for the parts of the titanium alloys complex that obtains and manufacture method thereof in CN200780047587.X, this by selecting surface treated titanium alloy member be combined with the injection of high rigidity Crystalline resin composition and improve the complex of its associativity, be adapted at the various electronic equipments needing Mobile portable to use, family's electrical article, Medical Devices, vehicle structural member, vehicle boarded articles for use, other electric component, use in corrosion resistance exterior member etc., the research of this technology is thought, for the character of titanium alloy base material, selecting suitably have crystalline resin combination (take polyphenylene sulfide as the 1st resin combination of main component, or with the 2nd resin combination that polybutylene terephthalate (PBT) resin is main component), directly be incorporated into by injection moulding on titanium alloy base material, titanium alloys parts and resin combination can be provided to be difficult to peel off and the complex be integrated.Also prove the research of this technology, if the resin combination difference (main component change) used, the adhesion of itself and titanium alloy member then obviously declines.
In the metal at present having had report and plastic material complex, focus mostly at hard colloid material to the selection of plastic material, such as crystal type (in other words not recommendations for selection amorphous materials) and there is suitable intensity, thus the air-tightness meeting the two faying face should provide the machinability of complex simultaneously.Further research also finds, for kind and the character of metal (metal material or alloy material), the selection of plastic material and the combined process of the two (injection moulding combined process) are selected, and all bring obvious Different Results to the characteristic of the complex finally obtained with the effect that can provide.
Summary of the invention
The invention provides the complex of a kind of metal and plastic cement, select flexible plastic cement/elastomer as the plastic material for connecting shaping, meeting between the two while bond strength, more can give this complex shock proof advantage, thus widening its application category.
Present invention also offers the manufacture method of the complex of described metal and plastic cement, for selected plastic material characteristic, coordinate shaping and treatment process accordingly, thus obtain metal and the excellent complex of plastic cement adhesion.
A kind of complex comprising metal material and plastic material provided by the invention, this complex is become at least part of region to have the hardware of nanoscale concaveconvex structure through chemical treatment faying face and plastic material is combined into, hardware and plastic material are combining closely of mosaic texture in this region, described hardware comprises metal material or alloy material component, the main component of described plastic material is polyether block amide, and this plastic material has individual layer or laminated construction.
Comprise the preparation method of the complex of metal material and plastic material described in present invention also offers, comprise following process:
At least part of region is become to be that the hardware base material of nanoscale concaveconvex structure is placed in the die cavity of mould through chemical treatment faying face;
In the die cavity of inserting described hardware base material, inject described plastic material and engage with hardware while making plastic material shaping, and hardware is combining closely of mosaic texture by described faying face and plastic material, obtains described complex.
In the solution of the present invention, select polyether-block-polyamide (PEBA) as the plastic material be combined with hardware, utilize its character having thermoplastic body and elastomer feature concurrently (or claiming flexible plastic cement), by the complex that suitable shaping combination technology and hardware are formed, the hardware making PEBA have nanoscale concaveconvex structure (surface is structured in other words) through chemical treatment with surface in forming process is mosaic texture at faying face and combines closely, not only there is excellent bond strength, for shell or the attaching parts of goods, the like product made compared to generally using ebonite material at present, more impart excellent impact resistance, when being incorporated into the surface of hardware, then while the sealing effectiveness of joint portion both realizing, also for this product provides shock resistance (such as shatter-resistant, put shock) effect, and when the structure member adopting complex of the present invention to make is for being assembled of product, be no matter between this complex or and other parts between, can both be easy to make the combination between parts can when without the need to ensureing compactness and seal when seal by " soft or hard collocation group connects " between parts, and such complex, can substitute in traditional handicraft, the effect that the assembly of multiple part reaches, and reach simultaneously and simplify product structure and optimize the effects such as volume.
On the other hand, the present invention also explores and adopts PEBA as in injected plastics material and metal (comprising metal or alloy) cohesive process, and the screening of material and mating between combined process, lay a good foundation for realizing continuous prodution.
Accompanying drawing explanation
Fig. 1 is the complex product schematic diagram that the embodiment of the present invention provides, and in figure, hardware and PEBA plastic cement to be formed by faying face through injection moulding combined process and combine closely.
Fig. 2 is the complex product schematic diagram with sandwich construction that the embodiment of the present invention provides, and while hardware is combined with PEBA plastic cement, another kind of macromolecular material is also by compound.
Fig. 3 is the complex product schematic diagram of the another kind of structure that the embodiment of the present invention provides, with the two kinds of macromolecular material compounds comprising PEBA plastic cement while of hardware.
Detailed description of the invention
The invention provides a kind of complex comprising metal material and plastic material, select the block copolymer mainly consisting of polyether block amide (PEBA) as the plastic material be combined with hardware, by inlaying combination in the concave-convex micro-structure of metal component surface, the complex adhesion obtained is strong, and while realization sealing, impact resistance gets a promotion.
The structure of polyether block amide can be expressed as: HO-(CO-PA-CO-PE-O) n-H, PA represents the unit of polyamide segment (also claiming nylon), PE represents the unit of polyethers, namely, in embodiment of the present invention, described polyether block amide is selected from the block copolymer be made up of polyamide segment and polyether segment, wherein amide units content is at least 10%, polyether block amide such as containing 30-90% amide units, have selected the polyether block amide plastic cement that amide units content is 30-60% in a particular embodiment.
In embodiment of the present invention, in the polyether block amide plastic material used, the number-average molecular weight 500-20000g/mol of polyether block amide.
Polyether block amide plastic material used in the present invention is all from commercial industrial products, namely, commercial PEBA, according to the application of complex and processing request, selection has the material of suitable polyamide-block (PA), to obtain required apparent hardness, in a particular embodiment, the PEBA material with PA6 block, PA66 block, PA12 block, PA11 block, PA12 block, PA6/11 block, PA6/12 block, PA610 block, PA1010 block equal-specification can be used.Commercially available or as required the architectural feature of described PEBA material is carried out synthesis and is obtained, and such as can use and be purchased nylon elastomer material PEBAX, its number-average molecular weight can be 700-16000g/mol.
Complex of the present invention is not particularly limited for combined hardware material, " hardware " described herein, unless otherwise stated, refer to that the component with predetermined structure or shape obtained processed by metal or alloy material through any feasible method, namely, the material of described hardware can comprise aluminum or aluminum alloy, magnesium or magnesium alloy, titanium or common material such as titanium alloy, copper or copper alloy or stainless steel etc., as long as its faying face can provide nanoscale concaveconvex structure.Further, complex provided by the invention, in order to provide enough bond strengths, require that the faying face of the hardware used becomes at least part of region for nanoscale concaveconvex structure through chemical treatment, its nanoscale concaveconvex structure shows as the pore structure that the gully structure of combining in length and breadth is formed, and aperture is 10-2000nm.In a particular embodiment, this nanoscale is concavo-convex can comprise and implement anodic oxidation to described faying face and corrosion micropore on the nano-pore that formed and anode oxide film extexine, described nano-pore aperture 10-100nm, described corrosion micropore size 100-2000nm.
PEBA embedded at the linear fraction of polyamide the block copolymer that polyether components (polyether units or polyether units sequence) obtains, softness two kinds of character of hard and polyethers (PE) material of polyamide (PA) material are had concurrently, it is a kind of two-phase structure body, be thermoplastic body (crystalline phase) and elastomer (amorphous phase), although this material causes the bond material as similar complex due to its special structure to have had research to think, based on all not recommendations of the performance in mechanical strength and water imbibition, but the research of inventor is thought, this characteristic of PEBA is used to combination technology and manufactures metal and plastic compound, can not only be formed with hardware and combine closely, when use this complex and other parts or material in conjunction with time, it is airtight in conjunction with problem that suitable flexible glue feature also solves between these different parts.Such as, during as mobile phone or the parts assembly of panel computer upper-lower casing, while the plastic cement of this complex self and metal can be combined closely, according to for the parts material characteristic of assembly, utilize plastic cement or metal as mating surface, " soft or hard collocation group connects " between wish assembly parts can be realized, can not need to introduce the third material or parts (such as binding agent or O type circle), not only promote the sealing effectiveness of assembly product, the minimizing of assembled material and operation, more brings the profitability of cost reduction and quality management and control.
It is that the plastic material of main component is combined closely by the patterned surface of hardware the formed body combining and obtain that complex of the present invention includes hardware and PEBA, can be the assembly parts for various kinds of equipment, device, its concrete shape and structure can according to the preprocessing of hardware and the uses of mould, and the manufacturing procedure of follow-up necessity meets.Especially may be used for assembling or assembly accuracy and compactness and require higher parts, such as the product of aforementioned " soft or hard collocation group connects ", also may be used for the product such as simultaneously needing electromagnetic shielding and insulation, the similar products such as such as radome.
For complex of the present invention, the PEBA plastic cement being incorporated into hardware can be through one-shot forming technique and the single layer structure formed, also can be the laminated construction that secondary or more time moulding process obtains, thus there is required profile or structure on the whole; Under the prerequisite not affecting molding effect; if add different colorants or characteristic auxiliary material (such as appropriate particulate or fibre object) to each PEBA material injected; then formed complex can show as the stack combinations of different color or figure or profile, also meets the needs to visual effect while promoting complex performance.
Complex of the present invention, the combination of hardware and PEBA plastic cement is by feasible moulding process, and PEBA plastic material is incorporated in the nanoscale concaveconvex structure of hardware faying face in forming process.Concrete moulding process, includes various mould molding technology, can include but not limited to the combination technologies such as injection mo(u)lding, extrusion molding, blow molding, leaching be molded.
In embodiment of the present invention, described shaping can be that thin material or many material are shaping, or, also can be that single or multiple is shaping.Such as, thin material or expect injection mo(u)lding more, or, single or multiple injection mo(u)lding.
In complex of the present invention, realize combining closely by the faying face of structuring process between hardware and plastic material, although hardware can be comprised after combining theoretically by the completely coated situation of plastic material, but as being used for the parts providing required goods with miscellaneous part assembly, it is that hardware has at least partial outer face not combine with plastic material that complex mentioned herein more embodies what have using value, use to provide lower procedure (or processing producer) as accessory, namely, the characteristics of components combined according to needing assembly, plastic layer or metal surface is selected to connect faying face as group during assembly.
Complex of the present invention can need according to design and use and comprise other plastic material in the structure further, namely, hardware and/or plastic material described in specific embodiment of the invention scheme can also by expect or repeatedly shaping and be combined with macromolecular material with the region be bonded to each other more, and the composition of described macromolecular material is not identical with described plastic material.Such as, hardware in conjunction with the region of described PEBA plastic cement or with the PEBA plastic surface of hardware through the complex of the connecting shaping such as injection moulding one, further combined with there being other macromolecular material, the stack combinations of such as different materials, thus there is wider use category.In conjunction with other macromolecular material can be the material completely not identical with performance with the composition of foregoing polyethers block amides, such as, can be ebonite material, resin material etc. conventional during current injection moulding combination technology is implemented, such as PPS, PBT, PA etc.In addition, according to specific embodiment of the invention scheme, in plastic material except as can also comprise except the PEBA of main component other complementary composition (submember) or claim additive, that is, the composition of plastic material of the present invention can also comprise fire retardant and/or reinforcing agent.Such as, UV light stabilizing agent can be added and increase the stable of the color of product under UV-irradiation and performance, or add the flame-retarding characteristic that fire retardant strengthens product, add the rigidity etc. of fiberglass reinforced product.Certainly, the adding proportion of these complementary compositions will be as the criterion with other physical property not affecting product adhesion performance and do not reduce product.Described additive can include but not limited to glass fibre, glass dust, bead, breeze, carbon fibre, carbon dust, metallic fiber etc.
The preparation method of metal of the present invention and plastic compound, at least include the hardware providing faying face to have described nanoscale concaveconvex structure through chemical treatment, and utilize described PEBA material in the mould of inserting described hardware, implement the technique combined.
According to embodiment of the present invention, the metal material preprocessing of selection is become the hardware of design shape and structure (also claiming hardware base material), and make the faying face of this hardware form described nanoscale concaveconvex structure through chemical treatment, embodiment all conventionally and can be had been reported and realize.Such as, the hardware base material shaping to preprocessing (being not limited to machining, casting, forging etc.) carries out chemical etching (corrosion) to form nano level concaveconvex structure by acid and/or alkali treatment in setting regions, or anodic oxidation is combined with chemical attack, obtains " the nano level concaveconvex structure " with spatial configuration by the oxidation film layer formed at substrate surface.This nanoscale is concavo-convex can be show as the pore structure that the gully structure of combining in length and breadth formed, and aperture is 10-2000nm.Concrete operations can by means such as masks, the superfine male and fomale(M&F) that length is 10-2000nm substantially can be gone out at the surface etching of hardware, these concaveconvex structures can not be separated but combine in length and breadth, form the structure of similar solution cavity, the plastic cement being beneficial to injection moulding enters and wherein makes with suitable crystal habit plastic material and hardware be formed at faying face to inlay combination.This nanoscale is concavo-convex also can be comprised and implement anodic oxidation to described faying face and corrosion micropore on the nano-pore that formed and anode oxide film extexine, described nano-pore aperture 10-100nm, described corrosion micropore size 100-2000nm.
Embodiment of the present invention comprise carries out chemical treatment at least part of region of the faying face of described hardware, to form nanoscale concaveconvex structure, described nanoscale concaveconvex structure shows as the pore structure that the gully structure of combining in length and breadth is formed, and aperture is 10-2000nm.
In a specific embodiment, described chemical treatment comprises the anode oxidation membrane first at least part of region of the faying face of hardware base material (setting surface) enforcement anodic oxidation formation to aperture 10-100nm nano-pore; Then chemical etching is carried out at least part of region of faying face after antianode oxidation processes, and forming aperture is that 100-2000nm corrodes micropore.
Above-mentioned nanoscale concaveconvex structure is formed about at hardware substrate surface, any known processing method and means can be adopted to realize, the present invention does not limit, such as, the method for above-mentioned formation nano-pore and corrosion micropore can realize with reference to the anodic oxidation recorded in CN103290449A and chemical attack operation.The concaveconvex structure of metal component surface exists in second hole folded structures mode, is more conducive to promote the bond strength with plastic body.
Embodiment of the present invention, for injection moulding combination technology, in injection step, can according to the character determination molding proces s parameters of used plastic material.In an embodiment, inject the injection temperature 210-270 DEG C during plastic material, injection pressure 8.0-11.0MPa, mold temperature 40-80 DEG C, cool after injection moulding completes, controlled cooling model speed 6-8 DEG C/sec, and the demoulding.Described Shooting Technique, can adopt method conventional in industry, such as, adopts injection screw injection moulding, according to the back segment of determined injection pressure setting screw rod, stage casing and nozzle exit pressure, also can adopt other any feasible injection moulding apparatus.
In the solution of the present invention, having injected the suitable method of rear employing makes shaping physical efficiency cool as early as possible, it is favourable for reaching desired crystallization effect to PEBA material, especially larger to overall volume composite article, such as, the cooling chamber that injection moulding completes backward injection mold leads to cold water and carrys out accelerating cooling.
More specifically in embodiment, the plastic material controlling molten state injects mould with the injection temperature of 230-250 DEG C, and mold temperature control 50-60 DEG C, after cooling, namely the demoulding obtains described complex.
The research of inventor also finds, the complex after cooling and demolding, through implementing hydrothermal treatment consists further, is beneficial to the bond strength promoting plastic material and hardware, that is, implements hydrothermal treatment consists under the condition that plastic material is suitable and can be beneficial to lifting adhesion.So specific embodiment of the invention scheme can also comprise and the complex completing injection moulding (such as injection mo(u)lding) is placed in the process that hot water carries out hydrothermal treatment consists, the water temperature 40-80 DEG C during hydrothermal treatment consists, processing time 8-12 hour.Such as, water temperature during hydrothermal treatment consists can be 50-60 DEG C, hydrothermal conditions 10-12 hours.
When preparing described composite article according to said method of the present invention, suitably adjust by the selection of technological parameter in the composition (in such as EBPA PA content) to raw material, each link and mate, being beneficial to the adhesion and other physical property that promote hardware and plastic material.Evaluating adhesion between hardware and plastic material can from two aspect: needed for the two separate, power is higher, and adhesion is better; When needing larger dynamics the two could be separated, the plastic cement observed on corrupt split face remains, and residual more obvious, adhesion is better.
Further, preparation method of the present invention is also included in and injects described plastic material and while making it be combined with described hardware or afterwards, by expecting to inject or repeatedly injection moulding technique more, described hardware and/or plastic material not with the region composite macromolecular material be bonded to each other, the composition of described macromolecular material is not identical with described plastic material.According to above-mentioned embodiment of the present invention, the complex obtained, meeting on the basis that hardware and PEBA plastic cement closely combine, also introduce the product of other macromolecular material through many material shaping (or repeatedly shaping), become and utilize different plastic cement hardware to be formed to the complex combining or have the different stack combinations of macromolecular material.Such as, by secondary or Multi-step injection molding, metal two sides of the complex obtained are made to be PEBA and a kind of hard plastic glue different with it (complex of such as Fig. 2 signal) respectively, certainly, making the complex (PEBA layer combines from hardware and different polymer material layers respectively as intermediate layer) of two kinds of different plastic cement lamination compounds, is also a kind of useful product form.
In sum, the invention provides a kind of different plastic cement (elastomer) material and corrupt split and shaping complex of adopting, by PEBA properties of materials, make this kind of complex product have larger room for promotion in application and effect, and there is good industrial applications prospect.
There is provided further instruction below in conjunction with specific embodiment to the present invention program and the beneficial effect that brings, but can not be interpreted as can any restriction of practical range to the present invention.
Embodiment one
1, the pretreatment of hardware
1) preprocessing of metal base and process
Commercially available aluminum alloy plate materials A1100, thick 1.5mm, be processed into the rectangle sheet material of several 50mmx10mm, grinding and polishing is placed in rinse bath, impregnated in the sodium hydrate aqueous solution of 40g/L after using absolute ethyl alcohol to clean, about 2-3min takes out, and dries, obtain the aluminium alloy flat substrates through decontamination degreasing with deionized water rinsing.
2) surface etching of metal base
It is the anodizing tank of 20wt% sulfuric acid that the aluminium alloy flat substrates more than completing decontamination ungrease treatment is put into containing concentration as anode, and electrolysis 10min at 20V voltage, 18-20 DEG C, takes out aluminum alloy sheet, dry up;
Obtained aluminum alloy sheet is soaked in (pH=12) in the sodium carbonate liquor of about 10wt%, 5-6min is soaked at 20 DEG C, complete the etching of antianode oxidation film layer, take out and fully wash oven dry with deionized water, obtain surface by the aluminum alloy base material of etch processes, whole process operation is not answered contaminated and again adheres to greasy dirt and other material.
Adopt the cross section of metallography microscope sem observation aluminum alloy sheet obtained above, the rete (aluminium oxide rete) being formed with 5mm left and right thickness on the surface of aluminum alloy sheet can be observed; Contain the nano-pore of 40-60nm with the rete inner surface that electron microscope can be observed aluminum alloy sheet surface, hole depth is about 1um; Electron microscope is adopted also to can be observed, there is the etch pit in 300-1000nm aperture on alloy sheet surface after etch processes, degree of depth 4um, for the pore structure that the gully structure of combining in length and breadth is formed, and can observe and there is double-hole structure in aluminum alloy surface, between the nano-pore of lower floor and the corrosion micropore on upper strata, there is connectivity structure.
2, injection moulding combined process
The above-mentioned aluminum alloy base material sheet completing surface etching process is embedded in injection forming mold, closing molding.PEBA is become melt and controls injection temperature, screw pressure and mold temperature, inject and inserted the mould of aluminum alloy base material, the PEBA melt injected is filled to the preset clearance between aluminum alloy base material and mould according to setting runner in mould, the cooling chamber that injection moulding completes backward mould passes into about 15 DEG C of cold water and cools injection molding body, controlled cooling model speed is about 7 DEG C/sec makes PEBA plastic cement solidify, the demoulding obtains required complex, and plastic material and aluminum alloy base material are closely as one.
For convenience of test, as shown in Figure 1, the two forward surface partly overlaps formation faying face the combination between hardware and PEBA.
3, the complex test sample completing the injection moulding demoulding is divided into two groups, and one group for subsequent use, and another group is inserted in 60 DEG C of hot water, is incubated 10 hours hydrothermal treatment consists.
According to aforesaid operations, the PEBA material of different composition is selected (to be specially PEBAX, commercially available nylon elastomer raw material A rkema series, number-average molecular weight 700-16000g/mol, following examples are identical) plastic material and determine injecting condition, obtain corresponding complex test sample, one by one to test sample do destructive testing, hardware is separated the required power applied by record with plastic layer, be recorded in table 1.
According to by the two separately required dynamics size and the destroyed degree of elastomer, evaluate bond strength to the complex material of each sample group, opinion rating is in table 2.
Table 1:
Note: the unit that the test in table applies power is MPa
1, after the sample demoulding, placement is tested after 12 hours-2 days;
2, hydro-thermal: the sample after the demoulding is inserted in the water of about 60 DEG C and is incubated 10 hours, places after taking out after 12 hours-2 days and tests.
Table 2:
Grade evaluation foundation in table 2:
C--elastomer needs comparatively great dynamics could separate with metal base, but destroyed, and has obvious elastomer to remain at metal base;
B-elastomer needs comparatively great dynamics could separate with metal base, but is not destroyed or has a small amount of destruction, does not substantially have elastomer to remain at metal base;
A-elastomer is easier to be separated with metal base.
According to the complex that the scheme of above example is made, when employing corresponding mould, just can obtain required product, according to the needs that it uses, the composition of adjustment PEBA elastomer material, such as add the additives such as appropriate glass fibre, carbon dust, can improve intensity and the anti-flammability of goods, the test of bond strength is similar with table 2 to table 1 with evaluation result.
According to the method described above, select corresponding mould, implement Multi-step injection molding technique (or expecting injection moulding) more, obtain multiple faying face of aluminum alloy base material and the composite article of elastomer-bonded, or the elastomer be combined with aluminum alloy base material is laminated construction.
Embodiment two
The selection of metal base (aluminium alloy) and pretreatment are all with embodiment one, elastomer is for being purchased Arkema4533, utilize Multi-step injection molding technique, first the complex of metal base and PEBA elastomer-bonded is obtained according to the method for embodiment one, then another kind of macromolecular material is used: commercially available PPSTOSOSGX-120 (the fiberglass reinforced body of polyphenylene sulfide) injection moulding again, makes the another side of metal base by plastic layers different in compound.
Select different moulds as required, the different faying face of the metal base that obtains respectively in conjunction with the complex of different materials plastic layer, as shown in Figure 2.
Similar operation, as shown in Figure 3, by expecting that injection moulding makes the zones of different of a certain faying face of metal base respectively in conjunction with the complex of different materials plastic layer more.
Embodiment three
Metal base is that magnesium alloy materials AZ91D, PEBA material is for being purchased Arkema4533.
Pretreatment and the embodiment one of metal base are similar, or conventionally, carry out surface anodization and chemical etching process, adopt metallographic microscope base material cross section, the rete (oxidation film layer) that its surface is formed with 5mm left and right thickness can be observed; Contain the nano-pore of 40-60nm with the rete inner surface that electron microscope can be observed its surface, hole depth is about 1um; Electron microscope is adopted also to can be observed, substrate surface after etch processes has the etch pit in 300-1000nm aperture, degree of depth 4um, for the pore structure that the gully structure of combining in length and breadth is formed, and double-hole structure can be observed, between the nano-pore of lower floor and the corrosion micropore on upper strata, there is connectivity structure.
The method recorded according to embodiment one carries out injection molding, obtains complex, sample sets 5.
Carry out bond strength test (destructive testing) and grade evaluation according to the method identical with embodiment one, result is listed in table 3 and table 4 respectively.
The bond strength of table 3 magnesium alloy and plastic compound
The bond strength grade evaluation of table 4 magnesium alloy and plastic compound

Claims (20)

1. one kind comprises the complex of metal material and plastic material, this complex is become at least part of region to have the hardware of nanoscale concaveconvex structure through chemical treatment faying face and plastic material is combined into, hardware and plastic material are combining closely of mosaic texture in this region, described hardware comprises metal material or alloy material component, the main component of described plastic material is polyether block amide, and this plastic material has individual layer or laminated construction.
2. complex according to claim 1, wherein, described polyether block amide is selected from the block copolymer be made up of polyamide segment and polyether segment, and amide units content is at least 10%.
3. complex according to claim 2, wherein, in described polyether block amide, amide units content is 30%--90%, more preferably 30-60%.
4. complex according to claim 1 and 2, wherein, the number-average molecular weight of described polyether block amide is 500-20000g/mol.
5. the complex according to any one of claim 1-3, wherein, the composition of described plastic material also comprises fire retardant and/or reinforcing agent.
6. complex according to claim 1, wherein, described hardware, faying face becomes at least part of region to be nanoscale concaveconvex structure through chemical treatment, its nanoscale concaveconvex structure shows as the pore structure that the gully structure of combining in length and breadth is formed, and aperture is 10-2000nm.
7. the complex according to claim 1 or 6, wherein, described hardware, faying face becomes at least part of region to be nanoscale concaveconvex structure through chemical treatment, this nanoscale concaveconvex structure comprises implements anodic oxidation to described faying face and corrosion micropore on the nano-pore that formed and anode oxide film extexine, described nano-pore aperture 10-100nm, described corrosion micropore size 100-2000nm.
8. complex according to claim 1, wherein, described metal material comprises aluminum or aluminum alloy, magnesium or magnesium alloy, titanium or titanium alloy, copper or copper alloy or stainless steel.
9. complex according to claim 1, wherein, described hardware and/or plastic material with the region be bonded to each other also by expecting or repeatedly mould molding and be combined with macromolecular material more, the composition of described macromolecular material is not identical with described plastic material.
10. complex according to claim 1, wherein, described plastic material is the laminated construction with multilayer, and the color between described multi-layer plastic material and/or shape are entirely not identical.
Comprise the preparation method of the complex of metal material and plastic material described in 11. any one of claim 1-10, comprise following process:
At least part of region is become to be that the hardware base material of nanoscale concaveconvex structure is placed in the die cavity of mould through chemical treatment faying face;
In the die cavity of inserting described hardware base material, inject described plastic material and combine with hardware while making plastic material shaping, and hardware is combining closely of mosaic texture by described faying face and plastic material, obtains described complex.
12. preparation methods according to claim 11, wherein, described hardware and plastic material realize through Shooting Technique combining, and the injection temperature 210-270 DEG C when injecting plastic material, injection pressure 8.0-11MPa, mold temperature 40-80 DEG C, cools after injection moulding completes, controlled cooling model speed 6-8 DEG C/sec.
13. preparation methods according to claim 11 or 12, wherein, also comprise and the complex completing injection mo(u)lding are placed in the process that hot water carries out hydrothermal treatment consists, the water temperature 40-80 DEG C during hydrothermal treatment consists, processing time 8-12 hour.Water temperature 50-60 DEG C during preferred water heat treatment.
14. preparation methods according to any one of claim 11-13, wherein, described in be cooled to water cooling.
15. preparation methods according to claim 11, wherein, also comprise and chemical treatment is carried out at least part of region of the faying face of described hardware, to form nanoscale concaveconvex structure, described nanoscale concaveconvex structure shows as the micropore that the gully structure of combining in length and breadth is formed, and aperture is 10-2000nm.
16. preparation methods according to claim 15, wherein, described chemical treatment comprises carries out etch processes to the faying face of hardware.
17. preparation methods according to claim 15, wherein, described chemical treatment comprises first to be implemented anodic oxidation at least part of region of the faying face of hardware base material and is formed and have the anode oxidation membrane that aperture is 10-100nm nano-pore; Then chemical etching is carried out at least part of region of faying face after antianode oxidation processes, and forming aperture is that 100-2000nm corrodes micropore.
18. preparation methods according to claim 11 or 12, wherein, being combined into thin material or expecting injection moulding more of described hardware and plastic material, or, for single or multiple is shaping.
19. preparation methods according to claim 11 or 18, wherein, also be included in and inject described plastic material and while making it be combined with described hardware or afterwards, by expecting or repeatedly moulding process more, described hardware and/or plastic material not with the region composite macromolecular material be bonded to each other, the composition of described macromolecular material is not identical with described plastic material.
20. preparation methods according to claim 11 or 18, wherein, implement many material and inject or repeatedly injection moulding technique, make plastic material be the laminated construction with multilayer, and color between described multi-layer plastic material and/or shape entirely not identical.
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